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1.
Int J Mol Sci ; 25(9)2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38731956

RESUMEN

X-ray fluorescence imaging (XFI) can localize diagnostic or theranostic entities utilizing nanoparticle (NP)-based probes at high resolution in vivo, in vitro, and ex vivo. However, small-animal benchtop XFI systems demonstrating high spatial resolution (variable from sub-millimeter to millimeter range) in vivo are still limited to lighter elements (i.e., atomic number Z≤45). This study investigates the feasibility of focusing hard X-rays from solid-target tubes using ellipsoidal lens systems composed of mosaic graphite crystals with the aim of enabling high-resolution in vivo XFI applications with mid-Z (42≤Z≤64) elements. Monte Carlo simulations are performed to characterize the proposed focusing-optics concept and provide quantitative predictions of the XFI sensitivity, in silico tumor-bearing mice models loaded with palladium (Pd) and barium (Ba) NPs. Based on simulation results, the minimum detectable total mass of PdNPs per scan position is expected to be on the order of a few hundred nanograms under in vivo conform conditions. PdNP masses as low as 150 ng to 50 ng could be detectable with a resolution of 600 µm when imaging abdominal tumor lesions across a range of low-dose (0.8 µGy) to high-dose (8 µGy) exposure scenarios. The proposed focusing-optics concept presents a potential step toward realizing XFI with conventional X-ray tubes for high-resolution applications involving interesting NP formulations.


Asunto(s)
Grafito , Grafito/química , Animales , Ratones , Imagen Óptica/métodos , Método de Montecarlo , Nanopartículas/química , Paladio/química , Simulación por Computador , Espectrometría por Rayos X/métodos
2.
Mikrochim Acta ; 191(6): 298, 2024 05 06.
Artículo en Inglés | MEDLINE | ID: mdl-38709403

RESUMEN

As a real-time fluid biopsy method, the detection of circulating tumor cells (CTCs) provides important information for the early diagnosis, precise treatment, and prognosis of cancer. However, the low density of CTCs in the peripheral blood hampers their capture and detection with high sensitivity and selectivity using currently available methods. Hence, we designed a sandwich-type electrochemical aptasensor that utilizes holothurian-shaped AuPd nanoparticles (AuPd HSs), tetrahedral DNA nanostructures (TDNs), and CuPdPt nanowire networks (NWs) interwoven with a graphdiyne (GDY) sheet for ultrasensitive non-destructive detection of MCF-7 breast cancer cells. CuPdPt NW-GDY effectively enhanced the electron transfer rate and coupled with the loaded TDNs. The TDNs could capture MCF-7 cells with precision and firmness, and the resulting composite complex was combined with AuPd HSs to form a sandwich-type structure. This novel aptasensor showed a linear range between 10 and 106 cells mL-1 and an ultralow detection limit of 7 cells mL-1. The specificity, stability, and repeatability of the measurements were successfully verified. Moreover, we used benzonase nuclease to achieve non-destructive recovery of cells for further clinical studies. According to the results, our aptasensor was more sensitive measuring the number of CTCs than other approaches because of the employment of TDNs, CuPdPt NW-GDY, and AuPd HSs. We designed a reliable sensor system for the detection of CTCs in the peripheral blood, which could serve as a new approach for cancer diagnosis at an early stage.


Asunto(s)
Aptámeros de Nucleótidos , Técnicas Biosensibles , ADN , Técnicas Electroquímicas , Oro , Límite de Detección , Nanopartículas del Metal , Células Neoplásicas Circulantes , Paladio , Células Neoplásicas Circulantes/patología , Humanos , Células MCF-7 , Nanopartículas del Metal/química , Técnicas Electroquímicas/métodos , Aptámeros de Nucleótidos/química , Oro/química , ADN/química , Técnicas Biosensibles/métodos , Paladio/química
3.
Environ Geochem Health ; 46(6): 200, 2024 May 02.
Artículo en Inglés | MEDLINE | ID: mdl-38696110

RESUMEN

Plant extracts are a great alternative to synthesizing nanoparticles of different metals and metal oxides. This green synthesis method has opened up numerous possibilities in various scientific domains. In present study, Leaf extract from Vitex negundo is a non-deciduous, long-lasting shrub from the Verbenaceae family is used as capping and reducing agents for the synthesis of silver and palladium nanoparticles. The characterization study UV-vis spectrophotometer analysis showed absorbance value around 320 nm which confirming that Ag-Pd nanoparticles have been successfully obtained. Further, SEM is used to investigate the morphology of Ag-Pd NPs, which revealing their spherical and rod-like configuration, aggregation, and the size of the particles are obtained between 50 and 100 nm. The successful synthesis of Ag-Pd NPs was further confirmed by the EDAX chart, which displayed the peak of Ag and Pd at bending energies between 0.5 and 1.5 keV. According to the quantitative study, Ag and Pd ions found about 5.24 and 13.28%, respectively. In addition, surface studies with TEM confirming that synthesized Ag-Pd NPs are predominates with spheres structure morphologies, with sizes averaging 11.20 nm and ranging from 10 to 20 nm. Further, Ag-Pd nanoparticles was applied as potential photocatalyst materials to degrade methylene blue dye and found about 85% of the degradation efficiency within 150 min of the sunlight exposure thus could be used as catalyst to removal of hazardous organic dye molecules.


Asunto(s)
Colorantes , Nanopartículas del Metal , Paladio , Plata , Vitex , Vitex/química , Paladio/química , Plata/química , Nanopartículas del Metal/química , Catálisis , Colorantes/química , Extractos Vegetales/química , Hojas de la Planta/química , Tecnología Química Verde , Fotólisis , Microscopía Electrónica de Transmisión
4.
Anal Chim Acta ; 1303: 342520, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38609255

RESUMEN

BACKGROUND: Cluster of Differentiation 44 (CD44) is considered an important biomarker for various cancers, and achieving highly sensitive detection of CD44 is crucial, which plays a significant role in tumor invasion and metastasis, providing essential information for clinical tumor diagnosis. Commonly used methods for analysis include fluorescence spectroscopy (FL), photoelectrochemical analysis (PEC), electrochemical analysis (EC), and commercial ELISA kits. Although these methods offer high sensitivity, they can be relatively complex to perform experimentally. Electrochemiluminescence (ECL) has gained widespread research attention due to its high sensitivity, ease of operation, effective spatiotemporal control, and close to zero background signal. RESULTS: In this work, a sandwich-type ECL immunosensor for detecting CD44 was constructed using luminol as a luminophore. In this sensing platform, bimetallic MOFs (Pd@FeNi-MIL-88B) loaded with palladium nanoparticles (Pd NPs) were used as a novel enzyme mimic, exhibiting excellent catalytic performance towards the electroreduction of H2O2. The hybrids provided a strong support platform for luminol and antibodies, significantly enhancing the initial ECL signal of luminol. Subsequently, core-shell Au@MnO2 nanocomposites were synthesised by gold nanoparticles (Au NPs) encapsulated in manganese dioxide (MnO2) thin layers, as labels. In the luminol/H2O2 system, Au@MnO2 exhibited strong light absorption in the broad UV-vis spectrum, similar to the black body effect, and the scavenging effect of Mn2+ on O2•-, which achieved the dual-quenching of ECL signal. Under the optimal experimental conditions, the immunosensor demonstrated a detection range of 0.1 pg mL-1 - 100 ng mL-1, with a detection limit of 0.069 pg mL-1. SIGNIFICANCE: Based on Pd@FeNi-MIL-88B nanoenzymes and Au@MnO2 nanocomposites, a dual-quenching sandwich-type ECL immunosensor for the detection of CD44 was constructed. The proposed immunosensor exhibited excellent reproducibility, stability, selectivity, and sensitivity, and provided a valuable analytical strategy and technical platform for the accurate detection of disease biomarkers, and opened up potential application prospects for early clinical treatment.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Neoplasias , Humanos , Compuestos de Manganeso , Oro , Peróxido de Hidrógeno , Luminol , Reproducibilidad de los Resultados , Inmunoensayo , Óxidos , Paladio , Receptores de Hialuranos
5.
Dalton Trans ; 53(18): 7922-7938, 2024 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-38644680

RESUMEN

The four new ligands, dialkyl esters of (S,S)-propylenediamine-N,N'-di-(2,2'-di-(4-hydroxy-benzil))acetic acid (R2-S,S-pddtyr·2HCl) (R = ethyl (L1), propyl (L2), butyl (L3), and pentyl (L4)) and corresponding palladium(II) complexes have been synthesized and characterized by microanalysis, infrared, 1H NMR and 13C NMR spectroscopy. In vitro cytotoxicity was evaluated using the MTT assay on four tumor cell lines, including mouse mammary (4T1) and colon (CT26), and human mammary (MDA-MD-468) and colon (HCT116), as well as non-tumor mouse mesenchymal stem cells. Using fluorescence spectroscopy were investigated the interactions of new palladium(II) complexes [PdCl2(R2-S,S-pddtyr)]; (R = ethyl (C1), propyl (C2), butyl (C3), and pentyl (C4)) with calf thymus human serum albumin (HSA) and DNA (CT-DNA). The high values of the binding constants, Kb, and the Stern-Volmer quenching constant, KSV, show the good binding of all complexes for HSA and CT-DNA. The mentioned ligands and complexes were also tested on in vitro antimicrobial activity against 11 microorganisms. Testing was performed by the microdilution method, where the minimum inhibitory concentration (MMC) and the minimum microbicidal concentration (MMC) were determined.


Asunto(s)
Antineoplásicos , Complejos de Coordinación , ADN , Ésteres , Paladio , Albúmina Sérica Humana , Paladio/química , Paladio/farmacología , Humanos , Animales , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , ADN/metabolismo , Ratones , Ésteres/química , Ésteres/farmacología , Albúmina Sérica Humana/química , Albúmina Sérica Humana/metabolismo , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Línea Celular Tumoral , Unión Proteica , Estructura Molecular , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Pruebas de Sensibilidad Microbiana
6.
Biosensors (Basel) ; 14(4)2024 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-38667165

RESUMEN

The exploration into nanomaterial-based nonenzymatic biosensors with superb performance in terms of good sensitivity and anti-interference ability in disease marker monitoring has always attained undoubted priority in sensing systems. In this work, we report the design and synthesis of a highly active nanocatalyst, i.e., palladium and platinum nanoparticles (Pt&Pd-NPs) decorated ultrathin nanoporous gold (NPG) film, which is modified on a homemade graphene paper (GP) to develop a high-performance freestanding and flexible nanohybrid electrode. Owing to the structural characteristics the robust GP electrode substrate, and high electrochemically catalytic activities and durability of the permeable NPG support and ultrafine and high-density Pt&Pd-NPs on it, the resultant Pt&Pd-NPs-NPG/GP electrode exhibits excellent sensing performance of low detection limitation, high sensitivity and anti-interference capability, good reproducibility and long-term stability for the detection of small molecular biomarkers hydrogen peroxide (H2O2) and glucose (Glu), and has been applied to the monitoring of H2O2 in different types of live cells and Glu in body fluids such as urine and fingertip blood, which is of great significance for the clinical diagnosis and prognosis in point-of-care testing.


Asunto(s)
Biomarcadores , Técnicas Biosensibles , Técnicas Electroquímicas , Oro , Grafito , Nanopartículas del Metal , Paladio , Platino (Metal) , Grafito/química , Oro/química , Platino (Metal)/química , Paladio/química , Nanopartículas del Metal/química , Biomarcadores/orina , Humanos , Peróxido de Hidrógeno , Aleaciones/química , Glucosa/análisis , Electrodos , Papel
7.
Cells ; 13(8)2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-38667306

RESUMEN

Several studies have reported the successful use of bio-orthogonal catalyst nanoparticles (NPs) for cancer therapy. However, the delivery of the catalysts to the target tissues in vivo remains an unsolved challenge. The combination of catalytic NPs with extracellular vesicles (EVs) has been proposed as a promising approach to improve the delivery of therapeutic nanomaterials to the desired organs. In this study, we have developed a nanoscale bio-hybrid vector using a CO-mediated reduction at low temperature to generate ultrathin catalytic Pd nanosheets (PdNSs) as catalysts directly inside cancer-derived EVs. We have also compared their biodistribution with that of PEGylated PdNSs delivered by the EPR effect. Our results indicate that the accumulation of PdNSs in the tumour tissue was significantly higher when they were administered within the EVs compared to the PEGylated PdNSs. Conversely, the amount of Pd found in non-target organs (i.e., liver) was lowered. Once the Pd-based catalytic EVs were accumulated in the tumours, they enabled the activation of a paclitaxel prodrug demonstrating their ability to carry out bio-orthogonal uncaging chemistries in vivo for cancer therapy.


Asunto(s)
Vesículas Extracelulares , Vesículas Extracelulares/metabolismo , Humanos , Animales , Catálisis , Ratones , Paclitaxel/farmacología , Paclitaxel/uso terapéutico , Paladio/química , Neoplasias/metabolismo , Neoplasias/tratamiento farmacológico , Neoplasias/patología , Línea Celular Tumoral , Distribución Tisular , Polietilenglicoles/química , Nanopartículas/química , Profármacos , Ratones Desnudos
8.
Dalton Trans ; 53(19): 8463-8477, 2024 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-38686752

RESUMEN

In continuation of our previous works on the cytotoxic properties of organopalladium compounds, in this contribution we describe the first systematic study of the anticancer activity of Pd(II)-aryl complexes. To this end, we have prepared and thoroughly characterized a wide range of palladium derivatives bearing different diphosphine, aryl and halide ligands, developing, when necessary, specific synthetic protocols. Most of the synthesized compounds showed remarkable cytotoxicity towards ovarian and breast cancer cell lines, with IC50 values often comparable to or lower than that of cisplatin. The most promising complexes ([PdI(Ph)(dppe)] and [PdI(p-CH3-Ph)(dppe)]), characterized by a diphosphine ligand with a low bite angle, exhibited, in addition to excellent cytotoxicity towards cancer cells, low activity on normal cells (MRC5 human lung fibroblasts). Specific immunofluorescence tests (cytochrome c and H2AX assays), performed to clarify the possible mechanism of action of this class of organopalladium derivatives, seemed to indicate DNA as the primary cellular target, whereas caspase 3/7 assays proved that the complex [PdI(Ph)(dppe)] was able to promote intrinsic apoptotic cell death. A detailed molecular docking analysis confirmed the importance of a diphosphine ligand with a reduced bite angle to ensure a strong DNA-complex interaction. Finally, one of the most promising complexes was tested towards patient-derived organoids, showing promising ex vivo cytotoxicity.


Asunto(s)
Antineoplásicos , Complejos de Coordinación , Simulación del Acoplamiento Molecular , Paladio , Fosfinas , Humanos , Paladio/química , Paladio/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Fosfinas/química , Fosfinas/farmacología , Ligandos , Relación Estructura-Actividad , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Línea Celular Tumoral , Ensayos de Selección de Medicamentos Antitumorales , Apoptosis/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Estructura Molecular
9.
Lab Chip ; 24(10): 2712-2720, 2024 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-38655620

RESUMEN

A colorimetric biosensor was elaboratively designed for fast, sensitive and multiplex bacterial detection on a single microfluidic chip using immune magnetic nanobeads for specific bacterial separation, immune gold@platinum palladium nanoparticles for specific bacterial labeling, a finger-actuated mixer for efficient immunoreaction and two coaxial rotatable magnetic fields for magnetic nanobead capture (outer one) and magnet-actuated valve control (inner one). First, preloaded bacteria, nanobeads and nanozymes were mixed through a finger actuator to form nanobead-bacteria-nanozyme conjugates, which were captured by the outer magnetic field. After the inner magnetic field was rotated to successively wash the conjugates and push the H2O2-TMB substrate for resuspending these conjugates, colorless TMB was catalyzed into blue TMBox products, followed by color analysis using ImageJ software for bacterial determination. This simple biosensor enabled multiplex Salmonella detection as low as 9 CFU per sample in 45 min.


Asunto(s)
Técnicas Biosensibles , Dispositivos Laboratorio en un Chip , Salmonella , Técnicas Biosensibles/instrumentación , Salmonella/aislamiento & purificación , Colorimetría/instrumentación , Oro/química , Técnicas Analíticas Microfluídicas/instrumentación , Paladio/química , Nanopartículas del Metal/química , Platino (Metal)/química
10.
J Hazard Mater ; 470: 134275, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38613954

RESUMEN

Palladium contaminants can pose risks to human health and the natural environment. Once Pd2+ enters the body, it can bind with DNA, proteins, and other macromolecules, disrupting cellular processes and causing serious harm to health. Therefore, it becomes critical to develop simple, highly selective and precise methods for detecting Pd2+in vivo. Here, we have successfully developed the first activated second near-infrared region fluorescence (NIR-II FL) and ratio photoacoustic (PA) probe NYR-1 for dual-modal accurate detection of Pd2+ levels. NYR-1 is capable of rapidly (< 60 s) and sensitively detection of Pd2+ in solution, providing switched on NIR-II FL920 and ratio PA808/PA720 dual-mode signal change. More notably, the probe NYR-1 was successfully used for non-invasive imaging of Pd2+ overload in mouse liver by NIR-II FL/Ratio PA dual-modality imaging technology for the first time. Thus, this work opens up a promising dual-modal detection method for the precise detection of Pd2+ in organisms and in the environment.


Asunto(s)
Colorantes Fluorescentes , Hígado , Paladio , Técnicas Fotoacústicas , Paladio/química , Animales , Hígado/diagnóstico por imagen , Hígado/metabolismo , Técnicas Fotoacústicas/métodos , Colorantes Fluorescentes/química , Ratones , Imagen Óptica , Rayos Infrarrojos , Ratones Endogámicos BALB C , Fluorescencia
11.
Anal Chim Acta ; 1305: 342582, 2024 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-38677838

RESUMEN

BACKGROUND: Detecting and neutralizing Pd2+ ions are a significant challenge due to their cytotoxicity, even at low concentrations. To address this issue, various chemosensors have been designed for advanced detection systems, offering simplicity and the potential to differentiate signals from different analytes. Nonetheless, these chemosensors often suffer from limited emission response and complex synthesis procedures. As a result, the tracking and quantification of residual palladium in biological systems and environments remain challenging tasks, with only a few chemosensing probes available for commercial use. RESULTS: In this paper, a straightforward approach for the selective detection of Pd2+ ions is proposed, which involves the design, synthesis, and utilization of a propargylated naphthalene-derived probe (E)-N'-((2-(prop-2-yn-1-yloxy)naphthalen-1-yl)methylene)benzohydrazide (NHP). The NHP probe exhibits sensitive dual-channel colorimetry and fluorescence Pd2+ detection over other tested metal ions. The detection process is performed through a catalytic depropargylation reaction, followed by an excited state intramolecular proton transfer (ESIPT) process, the detection limit is as low as 11.58 × 10-7 M under mild conditions. Interestingly, the resultant chemodosimeter adduct (E)-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide (NHH) was employed for the consecutive detection of CN- ions, exhibiting an impressive detection limit of 31.79 × 10-8 M. Validation of both detection processes was achieved through 1H nuclear magnetic resonance and density functional theory calculations. For real-time applications of the NHP and NHH probes, smartphone-assisted detection, and intracellular detection of Pd2+ and CN- ions within HeLa cells were studied. SIGNIFICANCE: This research presents a novel naphthalene derivative for visually detecting environmentally toxic Pd2+ and CN- ions. The synthesized probe selectively binds to Pd2+, forming a chemodosimeter. It successfully detects CN- ions through colorimetry and fluorimetry, offering a low detection limit and quick response. Notably, it's the first naphthalene-based small molecule to serve as a dual probe for toxic analytes - palladium and cyanide. Moreover, it effectively detects Pd2+ and CN- intracellularly in cancer cells.


Asunto(s)
Colorantes Fluorescentes , Paladio , Paladio/química , Humanos , Colorantes Fluorescentes/química , Colorantes Fluorescentes/síntesis química , Cianuros/análisis , Naftalenos/química , Naftalenos/toxicidad , Células HeLa , Imagen Óptica , Límite de Detección , Colorimetría/métodos , Estructura Molecular , Espectrometría de Fluorescencia
12.
Chem Commun (Camb) ; 60(36): 4838-4841, 2024 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-38619439

RESUMEN

Herein, we present an efficient Pd-catalysed method for stereoselective synthesis of chromone C-glycosides from various glycals. We successfully applied this method to various glycals with different protecting groups, yielding the corresponding glycosides in 41-78% yields. Additionally, we investigated the potential of this approach for the late-stage modification of natural products and pharmaceutical compounds linked to glycals, leading to the synthesis of their respective glycosides. Furthermore, we extended our research to gram-scale synthesis and demonstrated its applicability in producing various valuable products, including 2-deoxy-chromone C-glycosides. In summary, our work introduces a novel library of chromone glycosides, which holds promise for advancing drug discovery efforts.


Asunto(s)
Cromonas , Glicósidos , Paladio , Paladio/química , Catálisis , Glicósidos/química , Glicósidos/síntesis química , Estereoisomerismo , Cromonas/química , Cromonas/síntesis química , Estructura Molecular , Productos Biológicos/síntesis química , Productos Biológicos/química
13.
Microb Biotechnol ; 17(4): e14469, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38647123

RESUMEN

Owing to the increasing need for green synthesis and environmental protection, the utilization of biological organism-derived carbons as supports for noble-metal electrocatalysts has garnered public interest. Nevertheless, the mechanism by which microorganisms generate nanometals has not been fully understood yet. In the present study, we used genetically engineered bacteria of Shewanella oneidensis MR-1 (∆SO4317, ∆SO4320, ∆SO0618 and ∆SO3745) to explore the effect of surface substances including biofilm-associated protein (bpfA), protein secreted by type I secretion systems (TISS) and type II secretion systems (T2SS), and lipopolysaccharide in microbial synthesis of metal nanoparticles. Results showed Pd/∆SO4317 (the catalyst prepared with the mutant ∆SO4317) shows better performance than other biocatalysts and commercial Pd/C, where the mass activity (MA) and specific activity (SA) of Pd/∆SO4317 are 3.1 and 2.1 times higher than those of commercial Pd/C, reaching 257.49 A g-1 and 6.85 A m-2 respectively. It has been found that the exceptional performance is attributed to the smallest particle size and the presence of abundant functional groups. Additionally, the absence of biofilms has been identified as a crucial factor in the formation of high-quality bio-Pd. Because the absence of biofilm can minimize metal agglomeration, resulting in uniform particle size dispersion. These findings provide valuable mechanical insights into the generation of biogenic metal nanoparticles and show potential industrial and environmental applications, especially in accelerating oxygen reduction reactions.


Asunto(s)
Nanopartículas del Metal , Oxidación-Reducción , Oxígeno , Paladio , Shewanella , Shewanella/genética , Shewanella/metabolismo , Paladio/metabolismo , Paladio/química , Nanopartículas del Metal/química , Oxígeno/metabolismo , Ingeniería Genética , Microorganismos Modificados Genéticamente/genética , Microorganismos Modificados Genéticamente/metabolismo
14.
Mikrochim Acta ; 191(5): 280, 2024 04 22.
Artículo en Inglés | MEDLINE | ID: mdl-38649540

RESUMEN

An interfacial galvanic replacement strategy to controllable synthesize palladium nanoparticles (Pd NPs)-modified NiFe MOF nanocomposite on nickel foam, which served as an efficient sensing platform for quantitative determination of dopamine (DA). Pd NPs grown in situ on the nanosheets of NiFe MOF via self-driven galvanic replacement reaction (GRR) and well uniform distribution was achieved. This method effectively reduced the aggregation of metallic nanoparticles and significantly promoted the electron transfer rate during the electrochemical process, leading to improved electrocatalytic activity for DA oxidation. Remarkably, the precisely constructed biosensor achieved a low detection limit (LOD) of 0.068 µM and recovery of 94.1% (RSD 6.7%, N = 3) for simulated real sample detection and also exhibited superior selectivity and stability. The results confirmed that the as-fabricated Pd-NiFe/NF composite electrode could realize the quantitative determination of DA and showed promising prospects in real sample biosensing.


Asunto(s)
Técnicas Biosensibles , Dopamina , Técnicas Electroquímicas , Límite de Detección , Nanopartículas del Metal , Estructuras Metalorgánicas , Níquel , Paladio , Dopamina/análisis , Dopamina/química , Dopamina/sangre , Paladio/química , Níquel/química , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Estructuras Metalorgánicas/química , Técnicas Biosensibles/métodos , Nanopartículas del Metal/química , Electrodos , Oxidación-Reducción , Humanos
15.
Int J Biol Macromol ; 267(Pt 2): 131538, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38621572

RESUMEN

Lignin is continuously investigated by various techniques for valorization due to its high content of oxygen-containing functional groups. Catalytic systems employing hydrolysis­hydrogenolysis, leveraging the synergistic effect of redox metal sites and acid sites, exhibit efficient degradation of lignin. The predominance of either hydrolysis or hydrogenolysis reactions hinges upon the relative activity of acid and metal sites, as well as the intensity of the reductive atmosphere. In this study, the Pd-MoOx/TiO2 catalyst was found to primarily catalyze hydrolysis in the lignin depolymerization process, attributed to the abundance of moderate acidic sites on Pd and the redox-assisted catalysis of MoOx under inert conditions. After subjecting the reaction to 240 °C for 30 h, a yield of 48.22 wt% of total phenolic monomers, with 5.90 wt% consisting of diphenols, was achieved. Investigation into the conversion of 4-propylguaiacol (4-PG), a major depolymerized monomer of corncob lignin, revealed the production of ketone intermediates, a phenomenon closely linked to the unique properties of MoOx. Dehydrogenation of the propyl is a key step in initiating the reaction, and 4-PG could be almost completely transformed, accompanied by an over 97 % of 4-propylcatechol selectivity. This distinctive system lays a new theoretical groundwork for the eco-friendly valorization of lignin.


Asunto(s)
Lignina , Paladio , Titanio , Lignina/química , Hidrólisis , Catálisis , Titanio/química , Paladio/química , Hidrógeno/química , Molibdeno/química , Oxidación-Reducción , Óxidos/química
16.
Inorg Chem ; 63(18): 8449-8461, 2024 May 06.
Artículo en Inglés | MEDLINE | ID: mdl-38630518

RESUMEN

Developing synthetic supramolecular receptors to solubilize, scavenge, recognize, encapsulate, and sense steroids is challenging. Despite a limited number of receptors having affinity with steroids, none exists to bind steroidal bile acids selectively. Herein, we report a C2-symmetric metal-organic cage [Pd6L24]12+ and an expanded version of the Fujita cage [Pd6L14]12+, built with a conformationally flexible ligand L2, accessed through coordination-driven self-assembly. We examined both cages for steroid recognition in water: both have certain shared characteristics and distinctive features. [Pd6L14]12+ binds hydrophobic bile acids and other steroids by forming a 1:1 complex. In contrast, the expanded [Pd6L24]12+ cage exhibits an affinity for amphiphilic bile acids and selective steroids to encapsulate them as dimers, promoted by cooperative interguest hydrogen bonding. [Pd6L24]12+ has a 5 times stronger solubility enhancement ability for cholic acid compared to [Pd6L14]12+. Further, the expanded [Pd6L24]12+ cage can selectively sense bile acids in nanomolar detection limits through indicator displacement assay by employing sulforhodamine 101 (SR101).


Asunto(s)
Ácidos y Sales Biliares , Ácidos y Sales Biliares/química , Estructuras Metalorgánicas/química , Paladio/química , Estructura Molecular
17.
Talanta ; 274: 125934, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38574533

RESUMEN

Nowadays, novel and efficient signal amplification strategy in electrochemiluminescence (ECL) platform is urgently needed to enhance the sensitivity of biosensor. In this work, the dual ECL signal enhancement strategy was constructed by the interactions of Pd nanoparticles attached covalent organic frameworks (Pd NPs@COFs) with tris (bipyridine) ruthenium (RuP) and Exonuclease III (Exo.III) cycle reaction. Within this strategy, the COFs composite was generated from the covalent reaction between 2-nitro-1,4-phenylenediamine (NPD) and trialdehyde phloroglucinol (Tp), and then animated by glutamate (Glu) to attach the Pd NPs. Next, the "signal on" ECL biosensor was constructed by the coordination assembly of thiolation capture DNA (cDNA) onto the Pd NPs@COFs modified electrode. After the aptamer recognition of progesterone (P4) with hairpin DNA 1 (HP1), the Exo. III cycle reaction was initiated with HP2 to generate free DNA, which hybridized with cDNA to form double-stranded DNA (dsDNA). For that, the RuP was embedded into the groove of dsDNA and achieved the ultrasensitive detection of P4 with a lower limit of detection (LOD) down to 0.45 pM, as well as the excellent selectivity and stability. This work expands the COFs-based materials application in ECL signal amplification and valuable DNA cyclic reaction in biochemical testing field.


Asunto(s)
Técnicas Biosensibles , Técnicas Electroquímicas , Exodesoxirribonucleasas , Nanopartículas del Metal , Estructuras Metalorgánicas , Paladio , Progesterona , Nanopartículas del Metal/química , Estructuras Metalorgánicas/química , Paladio/química , Progesterona/análisis , Progesterona/química , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Exodesoxirribonucleasas/química , Exodesoxirribonucleasas/metabolismo , Límite de Detección , Mediciones Luminiscentes/métodos , Humanos , ADN/química
18.
J Environ Manage ; 358: 120910, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38636422

RESUMEN

Due to its unique physicochemical properties, palladium is widely used in several industry applications (e.g., vehicle emission control). In view of the circular economy, it is essential to explore secondary sources of palladium, such as urban mines. Current technologies for effective palladium recovery involve high energy consumption and severe environmental impact. More recently, a novel green method for recovering palladium from spent catalysts through a combination of mild acidic leaching and photodeposition on ZnO nanoparticles was proposed on a laboratory scale. In the present study, the environmental impacts of this recovery method, properly upscaled and modelled, was assessed by employing the LCA approach. Specifically, a comparative LCA was carried out for the process with as well as without recycling key components, such as Cu (II) and NaCl for the leaching solution and ZnO. The outcomes identified critical areas and drove the investigation of alternative process configurations to reduce its environmental footprint, such as the use of carbon dioxide in the photodeposition process with the aim of decreasing the resulting terrestrial ecotoxicity. This study marks a significant step forward in advancing research toward industrial-scale implementation of palladium recovery. It provides valuable insights for researchers in the field of green physicochemical processes for metal recovery, thus offering guidance for future decision-making towards more sustainable practices.


Asunto(s)
Paladio , Paladio/química , Catálisis , Reciclaje/métodos , Óxido de Zinc/química
19.
Biomater Adv ; 160: 213855, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38643692

RESUMEN

This research introduces a novel method that leverages Spirulina extract (S.E) as a bio-surfactant in the ultrasound-assisted synthesis (UAS) of Pd3+ (0.25-10 mol%) doped tin oxide (SnO2) self-assembled superstructures. Nanotechnology has witnessed significant advancements in recent years, driven by the exploration of novel synthesis methods and the development of advanced nanomaterials tailored for specific applications. Metal oxide nanoparticles, particularly SnO2, have garnered considerable attention due to their versatile properties and potential applications in various fields, including gas sensing, catalysis, and biomedical engineering. The study explores how varying influential parameters like S.E concentration, sonication time, pH, and sonication power can influence the resulting superstructures' morphology, size, and shape. A theoretical model for forming different hierarchical superstructures (HS) is proposed. X-ray diffraction (XRD) analysis confirms the crystalline tetragonal rutile phase of the SnO2:Pd HS. Raman spectroscopy reveals a red shift in the A1g mode, indicating phonon confinement due to various defects in the SnO2 structure. Further characterization using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) provides insights into particle size, surface morphology, elemental composition, and binding energy. The study also demonstrates the application of optimized SnO2:3Pd HS in developing latent fingerprints (LFPs) on different surfaces using a simple powder dusting (PD) method, with the fingerprints (FPs) visualized under normal light. A mathematical model developed in Python-based software is used to analyze various features of the developed FPs, including pore properties such as number, position, inter-spacing, area, and shape. Additionally, an in vitro MTT assay shows concentration-dependent anticancer activity of SnO2:3Pd nanoparticles (NPs) on MCF7 cell lines, highlighting their potential as a promising cancer treatment option. Overall, the study suggests that the optimized HS can serve as multifunctional platforms for biomedical and dermatoglyphics applications, demonstrating the versatility and potential of the synthesized materials.


Asunto(s)
Antineoplásicos , Paladio , Compuestos de Estaño , Compuestos de Estaño/química , Compuestos de Estaño/farmacología , Humanos , Paladio/química , Paladio/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Nanopartículas del Metal/química , Células MCF-7
20.
Chemosphere ; 356: 141857, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38570045

RESUMEN

Palladized iron (Pd/Fe) represents one of the most common modification strategies for nanoscale zero-valent iron (nZVI). Most studies prepared Pd/Fe by reducing iron salts and depositing Pd species on the surface of pre-synthesized nZVI, which can be called the two-step method. In this study, we proposed a one-step method to obtain Pd/Fe by the concurrent formation of Fe0 and Pd0 and investigated the effects of these two methods on 4-chlorophenol (4-CP) removal, with carboxymethylcellulose (CMC) coated as a surface modifier. Results indicated that the one-step method, not only streamlined the synthesis process, but also Pd/Fe-CMCone-step, synthesized by it, exhibited a higher 4-CP removal rate (97.9%) compared to the two-step method material Pd/Fe-CMCtwo-step (82.4%). Electrochemical analyses revealed that the enhanced activity of Pd/Fe-CMCone-step was attributed to its higher electron transfer efficiency and more available reactive species, active adsorbed hydrogen species (Hads*). Detection of intermediate products demonstrated that, under the influence of Pd/Fe-CMCone-step, the main route of 4-CP was through hydrodechlorination (HDC) to form phenol and H* was the main active specie, supported by EPR tests, quenching experiments and product analysis. Additionally, the effects of initial 4-CP concentration, initial pH, O2 concentration, anions such as Cl-, SO42-, HCO3-, and humic acid (HA) were also investigated. In conclusion, the results of this study suggest that Pd/Fe-CMCone-step, synthesized through the one-step method, is a convenient and efficient nZVI-modifying material suitable for the HDC of chlorinated organic compounds.


Asunto(s)
Carboximetilcelulosa de Sodio , Clorofenoles , Hierro , Paladio , Clorofenoles/química , Carboximetilcelulosa de Sodio/química , Hierro/química , Paladio/química , Contaminantes Químicos del Agua/química , Halogenación , Adsorción , Nanopartículas del Metal/química , Suspensiones
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